Synthesis, characterization and catalytic properties of pentafluorophenyl and sulfonated pentafluorophenyl ferroporphyrins

Author(s)

Daniela Gonçalves de Abreu

• Document type: Master's Dissertation
• Press: Ribeirão Preto.
• Institution: Universidade de São Paulo (USP). Faculdade de Filosofia, Ciências e Letras de Ribeirão Preto (PCARP/BC)
• Defense date: 2000-06-13

Examining board members

Yassuko Iamamoto; Marilda das Dores de Assis; Ana Maria da Costa Ferreira

• Advisor: Yassuko Iamamoto
• Field of knowledge: Physical Sciences and Mathematics - Chemistry
• Indexed in: Banco de Dados Bibliográficos da USP-DEDALUS
• Location: Universidade de São Paulo. Biblioteca Central do Campus de Ribeirão Preto; FFCLRP/Abreu, Daniela Gonçalves de

Abstract

The pentafluorophenyl substituted FeP present interesting catalytic properties. ln particular, the H2(TF15PP) and the H2(TF10PP) are precursors to obtention of anionic catalysts. ln this work, the synthesis optimisation of the H2(TF15PP) assymmetric porphyrin, was made varying amounts of reactants (pyrrole, pentafluorbenzaldehyde, benzaldehyde) and reaction conditions as temperature and oxidant. The total yields of the syntheses were calculated in an unpublished way in the group, through Nuclear Magnetic Ressonance. An extensive characterisation of the free-base porphyrins and the corresponding FeP was carried out through several techniques as spectroscopy of UV-Vis and IR, NMR 1H and 19F and also cyclic voltametry. A group -SO3- was put in the single phenyl group of the FeTF15PP and we could to get a pentafluorophenyl substituted anionic catalyst. The systematic study on the effect of the number of groups pentafluorophenyl in the catalytic activity of the FeP was carried out. ln this way, it were made oxidation reactions, using as substrate: cyclohexane and (Z)-cyclooctene and as catalyst: [Fe(TF5PP)]Cl, [Fe(TF15PP)]Cl and [Fe(TF15PPSO3Na)]Cl, in its monomeric and dimereric. Besides, the parallel mechanism with participation of oxygen was observed for FeTF15PP, but not for FeTF5PP and [Fe(TF15PPSO3Na)]Cl. We characterise the catalytic intermediates involved in oxidation reaction using the [Fe(TF5PP)] through EPR. The catalytic study together to the EPR data and cyclic voltametry was fundamental to understand the parallel mechanism with the participation of O2. (AU)